EP2386604A1 - Polyproylenflaschen - Google Patents

Polyproylenflaschen Download PDF

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Publication number
EP2386604A1
EP2386604A1 EP10160474A EP10160474A EP2386604A1 EP 2386604 A1 EP2386604 A1 EP 2386604A1 EP 10160474 A EP10160474 A EP 10160474A EP 10160474 A EP10160474 A EP 10160474A EP 2386604 A1 EP2386604 A1 EP 2386604A1
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EP
European Patent Office
Prior art keywords
propylene copolymer
polypropylene composition
polypropylene
comonomer content
fraction
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Granted
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EP10160474A
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English (en)
French (fr)
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EP2386604B1 (de
Inventor
Klaus Bernreitner
Petar Doshev
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Borealis GmbH
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Borealis GmbH
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Priority to EP10160474.2A priority Critical patent/EP2386604B1/de
Application filed by Borealis GmbH filed Critical Borealis GmbH
Priority to ES10160474T priority patent/ES2710606T3/es
Priority to RU2012148590/04A priority patent/RU2526260C2/ru
Priority to US13/642,007 priority patent/US8709561B2/en
Priority to PCT/EP2011/056001 priority patent/WO2011131578A1/en
Priority to CN201180020330.1A priority patent/CN102869719B/zh
Priority to AU2011244480A priority patent/AU2011244480C1/en
Priority to KR1020127030066A priority patent/KR101457779B1/ko
Publication of EP2386604A1 publication Critical patent/EP2386604A1/de
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Publication of EP2386604B1 publication Critical patent/EP2386604B1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7158—Bottles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention is directed to a new polypropylene composition suitable for the preparation of articles, like bottles, as well as to articles, i.e. bottles, made from the new polypropylene composition.
  • the extrusion blow molding process for instance is a very special process that allows in a flexible and cheap way the preparation of different kind of bottles with respect to size and shape.
  • Main drawback in this process is that the solidification step is very special compared to normal injection molding.
  • the surface property inside and/or outside of extrusion blown bottles is typically non-uniform (flow lines, melt fracture) leading to lower overall gloss and transparency compared to injection molded bottles or injection stretched blown molded articles (ISB.M).
  • ISB.M injection stretched blown molded articles
  • a certain improvement of the transparency can be achieved by visbreaking the polymer material but this concept has quite some limitation and is normally applied for relatively small bottles. Accordingly bigger bottles (volume of 11 or more) are preferably not producible with visbroken polypropylene in an extrusion blow molding process.
  • Beside gloss also impact is very important for the performance of a bottle. Higher impact reduces the risk of damages during transport of a bottle and is also important for the handling. The impact of bottles is reflected by the so called drop test.
  • the object of the present invention is to provide a polypropylene composition which enables inter alia the preparation of bottles by an extrusion blow molding process, wherein the bottles are featured by high gloss, high impact and optionally good stiffness behavior. Also processability of the polypropylene should be enhanced compared to known standard polypropylenes.
  • a random polypropylene must be combined with a branched polypropylene, like a Y/H-shaped polypropylene, i.e. a high melt strength polypropylene (HMS-PP) and an ⁇ -nucleating agent.
  • a branched polypropylene like a Y/H-shaped polypropylene, i.e. a high melt strength polypropylene (HMS-PP) and an ⁇ -nucleating agent.
  • HMS-PP high melt strength polypropylene
  • the present invention is directed in a first aspect to a polypropylene composition having a melt flow rate MFR 2 (230 °C) measured according to ISO 1133 of at least 2.0 g/10min, said polypropylene composition comprises a propylene copolymer (C-PP), a high melt strength polypropylene (HMS-PP), and an ⁇ -nucleating agent (N), wherein the propylene copolymer (C-PP)
  • the propylene copolymer (C-PP) fulfills the equation (I) R + 4.96 x C ⁇ 95.66 wherein R is the randomness [%] measured by Fourier transform infrared spectroscopy (FTIR), and C is the comonomer content [wt.-%] measured by Fourier transform infrared spectroscopy (FTIR).
  • FTIR Fourier transform infrared spectroscopy
  • the present invention is directed to a polypropylene composition having a melt flow rate MFR 2 (230 °C) measured according to ISO 1133 of at least 2.0 g/10min, said polypropylene composition comprises a propylene copolymer (C-PP), a high melt strength polypropylene (HMS-PP), and an ⁇ -nucleating agent (N), wherein the propylene copolymer (C-PP)
  • the propylene copolymer (C-PP) according to the second aspect comprises two propylene copolymer fractions (A) and (B), wherein the comonomer content of the first propylene copolymer fraction (A) is in the range of 1.0 to 4.5 wt.-% and the comonomer content of the first propylene copolymer fraction (A) is lower compared to the comonomer content of the second propylene copolymer fraction (B).
  • the polypropylene composition according to the first or second aspect preferably comprises as polymer components only the propylene copolymer (C-PP) and the high melt strength polypropylene (HMS-PP) as defined above and in further detail below.
  • C-PP propylene copolymer
  • HMS-PP high melt strength polypropylene
  • polypropylene composition has superior properties compared to known polypropylene compositions, in particular to those normally used for extrusion blown molding processes.
  • the polypropylene composition of the present invention enables in particular to produce extrusion blown bottles with high gloss, exceptional impact according to the drop test and good stiffness. Also the processability is improved due to the higher melt flow rate in view of the comparative examples (see experimental part).
  • the melt flow rate mainly depends on the average molecular weight. This is due to the fact that long molecules render the material a lower flow tendency than short molecules.
  • An increase in molecular weight means a decrease in the MFR-value.
  • the melt flow rate (MFR) is measured in g/10 min of the polymer discharged through a defined die under specified temperature and pressure conditions and the measure of viscosity of the polymer which, in turn, for each type of polymer is mainly influenced by its molecular weight but also by its degree of branching.
  • the melt flow rate measured under a load of 2.16 kg at 230 °C (ISO 1133) is denoted as MFR 2 (230 °C).
  • the inventive polypropylene composition has an MFR 2 (230 °C) of at least 2.0 g/10min, more preferably of at least 2.2 g/10min. Accordingly it is in particular appreciated that the inventive polypropylene composition has an MFR 2 (230 °C) in the range of 2.0 to 6.0 g/10 min, more preferably of 2.1 to 4,5 g/10 min, still more preferably of 2.2 to 3,8 g/10 min.
  • the new polypropylene composition must comprise a high melt strength polypropylene (HMS-PP).
  • HMS-PP high melt strength polypropylene
  • the polypropylene composition is further characterized by a strain hardening behavior with a haul-off force F max as determined in the Rheotens at 200 °C of at least 7.0 cN and a draw down velocity v max of at least 180 mm/s, more preferably by a strain hardening behavior with a haul-off force F max of at least 7.5 cN and a draw down velocity v max of at least 185 mm/s.
  • the polypropylene composition can be additionally defined by the gel content.
  • the gel content is a good indicator for the chemical modification of the polypropylene composition or its components. Accordingly the present invention is featured by relatively moderate gel content, i.e. of not more than 1.00 wt.-%, even more preferred of not more than 0.80 wt.-%, still more preferred of not more than 0.50 wt.-% determined as the relative amount of polymer insoluble in boiling xylene (xylene hot insoluble fraction, XHI).
  • the polypropylene composition must comprise a certain amount of high melt strength polypropylene (HMS-PP).
  • the amount of gel content in the polypropylene composition is preferably more than 0.15 wt.-%, more preferably of at least 0.27 wt.-%.
  • a preferred range for the gel content of the polypropylene composition is 0.05 to 0.90 wt.-%, like 0.15 to 0.90 wt.-%, more preferred 0.26 to 0.8 wt.-%.
  • the present polypropylene composition has preferably a xylene cold soluble fraction (XCS) of not more than 15.0 wt-%, more preferably of not more than 14.0 wt.-%, yet more preferably of not more than 12.0 wt.-%, like not more than11.5 wt.-%.
  • XCS xylene cold soluble fraction
  • the polypropylene composition can be specified by the amount of comonomer units other than propylene within the polypropylene composition. Accordingly it is appreciated that the amount of units derived from C 2 to C 12 ⁇ -olefins other than propylene is not more than 7.0 wt.-%, preferably not more than 6.0 wt.-%, like not more than 5.5 wt.-%, in the polypropylene composition.
  • polypropylene composition is further defined by the polymer components within the composition.
  • the propylene copolymer (C-PP) comprises units derived from propylene and at least another C 2 to C 12 ⁇ -olefin, preferably at least another C 2 to C 10 ⁇ -olefin. Accordingly the propylene copolymer (C-PP) comprises units derived from propylene and at least another ⁇ -olefin selected from the group consisting of ethylene C 4 ⁇ -olefin, C 5 ⁇ -olefin, C 6 ⁇ -olefin, C 7 ⁇ -olefin, C 8 ⁇ -olefin, C 9 ⁇ -olefin and C 10 ⁇ -olefin.
  • the propylene copolymer (C-PP) comprises units derived from propylene and at least another ⁇ -olefin selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene, wherein ethylene, 1-butene and 1-hexene are preferred. It is in particular preferred that the propylene copolymer (C-PP) consists of units derived from propylene and ethylene.
  • the amount of units derived from C 2 to C 12 ⁇ -olefins other than propylene in the propylene copolymer (C-PP) is equal or below 7.0 wt.-%, preferably in the range of 1.0 to 7.0 wt.-%, more preferably 1.5 to 6.0 wt.-%, still more preferably 2.0 to 5.5 wt.-%.
  • the propylene copolymer (C-PP) is a random propylene copolymer.
  • the term random is understood according to IUPAC (Glossary of basic terms in polymer science; IUPAC recommendations 1996). Accordingly it is preferred that the propylene copolymer (C-PP) has a randomness of at least 40 %, more preferably of at least 50 %, yet more preferably at least 55 %, even more preferably of at least 60 %, and still more preferably of at least 65 %.
  • the propylene copolymer (C-PP) fulfills the equation (I), yet more preferably fulfills the equation (Ia), yet more preferably fulfills the equation (Ib), R + 4.96 x C ⁇ 95.66 R + 4.30 x C ⁇ 94.66 R + 4.30 x C ⁇ 93.66 wherein R is the randomness [%] measured by Fourier transform infrared spectroscopy (FTIR), and C is the comonomer content [wt.-%] measured by Fourier transform infrared spectroscopy (FTIR).
  • FTIR Fourier transform infrared spectroscopy
  • propylene copolymer (C-PP) is isotactic. Accordingly it is appreciated that propylene copolymer (C-PP) has a rather high isotactic triad concentration, i.e. higher than 90 %, more preferably higher than 92 %, still more preferably higher than 93 % and yet more preferably higher than 95 %, like higher than 97 %.
  • the xylene soluble content of the propylene copolymer (C-PP) is a rather low.
  • the propylene copolymer (C-PP) has preferably a xylene cold soluble fraction (XCS) measured according to ISO 6427 (23 °C) of not more than 15.0 wt-%, more preferably of not more than 13.0 wt.-%, yet more preferably of not more than 12.0 wt.- %, like not more than11.5 wt.-%.
  • XCS xylene cold soluble fraction measured according to ISO 6427 (23 °C) of not more than 15.0 wt-%, more preferably of not more than 13.0 wt.-%, yet more preferably of not more than 12.0 wt.- %, like not more than11.5 wt.-%.
  • XCS xylene cold soluble fraction
  • the propylene copolymer (C-PP) is multimodal, like bimodal in view of the molecular weight distribution and/or the comonomer content distribution, the latter especially preferred.
  • multimodal or “bimodal” used herein refers to the modality of the polymer, i. e.
  • the polymer fractions of the the propylene copolymer (C-PP) can be produced in a sequential step process, using reactors in serial configuration and operating at different reaction conditions. As a consequence, each fraction prepared in a specific reactor will have its own molecular weight distribution and/or comonomer content distribution.
  • the propylene copolymer (C-PP) may be multimodal, like bimodal, in view of the comonomer content and/or molecular weight. It is in particular appreciated that the the propylene copolymer (C-PP) is multimodal, like bimodal, in view of the comonomer content.
  • the propylene copolymer (C-PP) is of multimodal, like bimodal, character, in particular multimodal, like bimodal, in view of the comonomer content
  • the individual fractions are present in amounts influencing the properties of the material. Accordingly it is appreciated that each of these fractions is at least present in the amount of 10 wt.-% based on the propylene copolymer (C-PP). Accordingly in case of a bimodal system, in particular in view of the comonomer content, the split of the two fractions is preferably 40:60 to 60:40.
  • the propylene copolymer (C-PP) comprises at least, preferably consists of, two propylene copolymer fractions (A) and (B) which differ in their comonomer content, like ethylene content (preferably as the only comonomer in the propylene copolymer (C-PP)), wherein the first propylene copolymer fraction (A) is present from 40 to 60 wt.-% and the second propylene copolymer fraction (B) from 60 to 40 wt.-% (40:60 to 60:40).
  • both propylene copolymer fractions (A) and (B) comprise, preferably consists of, units derived from propylene and at least another C 2 to C 12 ⁇ -olefin, preferably at least another C 2 to C 10 ⁇ -olefin.
  • the two propylene copolymer fractions (A) and (B) comprise, preferably consist of, units derived from propylene and at least another ⁇ -olefin selected from the group consisting of ethylene, C 4 ⁇ -olefin, C 5 ⁇ -olefin, C 6 ⁇ -olefin, C 7 ⁇ -olefin, C 8 ⁇ -olefin, C 9 ⁇ -olefin and C 10 ⁇ -olefin.
  • the two propylene copolymer fractions (A) and (B) comprise, preferably consist of, units derived from propylene and at least another ⁇ -olefin selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene, wherein ethylene, 1-butene and 1-hexene are preferred. It is in particular preferred that the two propylene copolymer fractions (A) and (B) consist of units derived from propylene and ethylene. It is especially preferred that the comonomers within the two propylene copolymer fractions (A) and (B) are the same.
  • the propylene copolymer (C-PP) comprises, preferably consists of, the two propylene copolymer fractions (A) and (B), wherein the two propylene copolymer fractions (A) and (B) have the same comonomers like ethylene, i.e. the propylene copolymer fractions (A) and (B) consist of units deravible from propylene and ethylene only.
  • both fractions (A) and (B) are propylene copolymers.
  • the comonomer content of the first propylene copolymer fraction (A) is in the range of 1.0 to 4.5 wt.-%, more preferably is in the range of of 1.5 to 3.5 wt.-%, like 1.8 to 3.2 wt.-%.
  • the comonomer content of the first propylene copolymer fraction (A) is lower compared to the comonomer content of the second propylene copolymer fraction (B).
  • the comonomer content, like ethylene content, of the second propylene copolymer fraction (B) is at least 1.0 wt.-%, more preferably at least 1.5 wt.-%, yet more preferably at least 2.0 wt.-%, higher than the comonomer content, like ethylene content, of the first propylene copolymer fraction (A).
  • the difference in the comonomer content between the two fractions should be not too high, i.e. not higher than 6.0 wt.-%, preferably not higher than 5.0 wt%, more preferably not higher than 4.7 wt.-%, to avoid any separation tendencies.
  • the comonomer content, like ethylene content, of the second propylene copolymer fraction (B) is preferably 1.0 to 7.0 wt.- %, more preferably of 1.2 to 7.0 wt.-% higher than the comonomer content, like ethylene content, of the first propylene copolymer fraction (A).
  • the second propylene copolymer fraction (B) has comonomer content, like ethylene content, of at least 3.0 wt.-%, more preferably of at least 4.0 wt.-%, like at least 5.0 wt.-%, yet more preferably in the range of 3.0 to 10.0 wt.-%, like 3.0 to 9.0 wt.-%, still more preferably in the range of 4.0 to 8.5 wt.-%
  • the propylene copolymer (C-PP) has a rather high crystallization temperature Tc measured by differential scanning calorimetry (DSC) of at least 110 °C, even more preferably of at least 115 °C.
  • this crystallization temperature Tc is measured before degradation of the polypropylene composition and thus before degradation of the propylene copolymer (C-PP).
  • the propylene copolymer (C-PP) is ⁇ -nucleated, i.e. comprises the ⁇ -nucleating agent (N) as defined in detail below.
  • the inventive polypropylene composition must at least comprise - as polymer components - a propylene copolymer (C-PP) and a high melt strength polypropylene (HMS-PP).
  • the two components must be chosen in such a way that in particular the required MFR 2 (230 °C) of at least 2.0 g/10min for the final polypropylene composition is met.
  • MFR 2 230 °C
  • HMS-PP high melt strength polypropylene
  • An alternative route is to take a propylene copolymer (C-PP) having a significantly lower MFR 2 (230 °C) compared to the final product, degrading said propylene copolymer (C-PP), i.e. visbreaking, said propylene copolymer (C-PP), and subsequently mixing it with the high melt strength polypropylene (HMS-PP).
  • a further option is to use a mixture of a propylene copolymer (C-PP) and the high melt strength polypropylene (HMS-PP) (optionally with the ⁇ -nucleating agent (N)), wherein said propylene copolymer (C-PP) has a significantly lower MFR 2 (230 °C) compared to the final product. Said mixture is visbroken by using peroxide to the required MFR 2 (230 °C) of at least 2.0 g/10min for the final polypropylene composition. The latter option is the most preferred.
  • the propylene copolymer (C-PP) within the polypropylene composition has preferably an MFR 2 (230 °C) of not more than 4.5 g/10min. More preferably the propylene copolymer (C-PP) within the polypropylene composition has an MFR 2 (230 °C) of not more than 3.0 g/10min.
  • the propylene copolymer (C-PP) within the polypropylene composition has an MFR 2 (230 °C) in the range of 2.0 to 4.5 g/10 min, more preferably of 2.1 to 3.8 g/10 min, still more preferably of 2.2 to 3.5 g/10 min.
  • the used propylene copolymer (C-PP) has an MFR 2 (230 °C) of at least 0.3 g/10min, more preferably in the range of 0.5 to 3.0 g/10min, yet more preferably of 1.0 to 2.5 g/10min, like 1.3 to 2.0 g/10min.
  • the initially used propylene copolymer (C-PP) is chosen in such a manner that the visbreaking ratio (final MFR 2 (230 °C) / initial MFR 2 (230 °C)) is 1.3 to 3.0, more preferably 1.4 to 2.5, wherein “initial MFR 2 (230 °C)” is the MFR 2 (230 °C) of the propylene copolymer (C-PP) before visbreaking and “final MFR 2 (230 °C)” is the MFR 2 (230 °C) of the propylene copolymer (C-PP) after visbreaking and/or the MFR 2 (230 °C) of the polypropylene composition after visbreaking.
  • the visbreaking ratio final MFR 2 (230 °C) / initial MFR 2 (230 °C)
  • HMS-PP high melt strength polypropylene
  • polymer types are characterized by a certain degree of branching.
  • Possible high melt strength polypropylenes (HMS-PP) are so called Y/H-polypropylenes and for instance described in EP 0 787 750 , i.e. single branched polypropylene types (Y polypropylenes having a backbone with a single long side-chain and an architecture resembles a "Y”) and polypropylene types in which polymer chains are coupled with a bridging group (an architecture resembles a "H”).
  • Such polypropylenes are characterized by rather high melt strength.
  • a parameter of the degree of branching is the branching index g'.
  • the branching index g' correlates with the amount of branches of a polymer.
  • a low g'-value is an indicator for a high branched polymer.
  • the branching index g' of the high melt strength polypropylene shall be less than 1.0, more preferably equal or less than 0.9, like less than 0.8. In another preferred embodiment the branching index g' of the high melt strength polypropylene (HMS-PP) shall be preferably less than 0.7.
  • the high degree of branching of the high melt strength polypropylene (HMS-PP) contributes also to its melt strength. Accordingly it is preferred that the high melt strength polypropylene (HMS-PP) is further characterized by a strain hardening behavior with a haul-off force F max of at least 10.0 cN and a draw down velocity v max of at least 200 mm/s, more preferably by a strain hardening behavior with a haul-off force F max of at least 20.0 cN and a draw down velocity v max of at least 250 mm/s, yet more preferably by a strain hardening behavior with a haul-off force F max of at least 25.0 cN and a draw down velocity v max of at least 250 mm/s.
  • Such a high melt strength polypropylene is preferably obtained by modifying, i.e. chemically modifying, a polypropylene. Such a modification is necessary to achieve the branching structure and/or the strain hardening phenomena of the high melt strength polypropylene (HMS-PP). Such a modification has also influence on the gel content of the high melt strength polypropylene (HMS-PP). Accordingly it is justified to define the high melt strength polypropylene (HMS-PP) further and/or alternatively by its gel content. Thus it is appreciated that the high melt strength polypropylene (HMS-PP) is featured by a relatively moderate gel content, i.e.
  • the high melt strength polypropylene may show a certain degree of branching and thus a certain amount of gel content, i.e. of at least 0.15 wt.-%, more preferably of at least 0.27 wt.-%.
  • a preferred range for the gel content of the high melt strength polypropylene (HMS-PP) is 0.05 to 0.90 wt.-%, more preferred 0.26 to 0.8 wt.-%.
  • melt strength polypropylene has an MFR 2 (230 °C) in a range of 1.0 to 10.0 g/10 min, more preferably of 4.0 to 8.5 g/10 min, still more preferably of 6.0 to 8.0 g/10 min.
  • the high melt strength polypropylene has a density of at least 850 kg/m 3 , more preferably of at least 875 kg/m 3 and most preferably of at least 900 kg/m 3 .
  • the high melt strength polypropylene has a density of not more than 950 kg/m 3 , more preferably of not more than 925 kg/m 3 and most preferably of not more than 910 kg/m 3 .
  • the high melt strength polypropylene has a melting point of at least 140°C, more preferably of at least 150°C and most preferably of at least 160°C.
  • melt strength polypropylene is preferably a modified polypropylene. Accordingly the melt strength polypropylene (HMS-PP) can be further defined by the way obtained.
  • the melt strength polypropylene (HMS-PP) is preferably the result of treating an unmodified polypropylene (A) with thermally decomposing radical-forming agents and/or with ionizing radiation.
  • the modification is accomplished by the use of bifunctionally unsaturated monomer(s) and/or multifunctionally unsaturated low molecular weight polymer(s) as chemically bound bridging unit(s).
  • HMS-PP melt strength polypropylene
  • EP 0 787 750 EP 0 879 830 A1 and EP 0 890 612 A2 . All documents are herewith included by reference.
  • the amount of peroxide is preferably in the range of 0.05 to 3.00 wt.-% based on the unmodified polypropylene (A).
  • the high melt strength polypropylene comprises units derived from
  • Bifunctionally unsaturated or multifunctionally unsaturated as used above means preferably the presence of two or more non-aromatic double bonds, as in e.g. divinylbenzene or cyclopentadiene or polybutadiene. Only such bi- or multifunctionally unsaturated compounds are used which can be polymerized preferably with the aid of free radicals. The unsaturated sites in the bi- or multifunctionally unsaturated compounds are in their chemically bound state not actually "unsaturated", because the double bonds are each used for a covalent bond to the polymer chains of the polypropylene (A).
  • Reaction of the bifunctionally unsaturated monomer(s) and/or multifunctionally unsaturated low molecular weight polymer(s), preferably having a number average molecular weight (M n ) ⁇ 10000 g/mol, synthesized from one and/or more unsaturated monomers with the propylene polymer composition may be performed in the presence of a thermally free radical forming agent, e. g. decomposing free radical-forming agent, like a thermally decomposable peroxide and/or ionizing radiation or microwave radiation.
  • a thermally free radical forming agent e. g. decomposing free radical-forming agent, like a thermally decomposable peroxide and/or ionizing radiation or microwave radiation.
  • the bifunctionally unsaturated monomers may be any organic compound having the same functionality as the bifunctionally unsaturated monomers.
  • Especially preferred bifunctionally unsaturated monomers are 1,3-butadiene, isoprene, dimethyl butadiene and divinylbenzene.
  • the multifunctionally unsaturated low molecular weight polymer preferably having a number average molecular weight (M n ) ⁇ 10000 g/mol may be synthesized from one or more unsaturated monomers.
  • a preferred low molecular weight polymer is polybutadiene, in particular a polybutadiene having more than 50.0 wt.-% of the butadiene in the 1,2-(vinyl) configuration.
  • the high melt strength polypropylene may contain more than one bifunctionally unsaturated monomer and/or multifunctionally unsaturated low molecular weight polymer. Even more preferred the amount of bifunctionally unsaturated monomer(s) and multifunctionally unsaturated low molecular weight polymer(s) together in the high melt strength polypropylene (HMS-PP) is 0.01 to 10.0 wt.-% based on said high melt strength polypropylene (HMS-PP).
  • bifunctionally unsaturated monomer(s) and/or multifunctionally unsaturated low molecular weight polymer(s) are used in the presence of a thermally decomposing free radical-forming agent.
  • Peroxides are preferred thermally decomposing free radical-forming agents. More preferably the thermally decomposing free radical-forming agents are selected from the group consisting of acyl peroxide, alkyl peroxide, hydroperoxide, perester and peroxycarbonate.
  • Acyl peroxides benzoyl peroxide, 4-chlorobenzoyl peroxide, 3-methoxybenzoyl peroxide and/or methyl benzoyl peroxide.
  • Alkyl peroxides allyl t-butyl peroxide, 2,2-bis(t-butylperoxybutane), 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(t-butylperoxy) valerate, diisopropylaminomethyl-t-amyl peroxide, dimethylaminomethyl-t-amyl peroxide, diethylaminomethyl-t-butyl peroxide, dimethylaminomethyl-t-butyl peroxide, 1,1-di-(t-amylperoxy)cyclohexane, t-amyl peroxide, t-butylcumyl peroxide, t-butyl peroxide and/or 1-hydroxybutyl n-butyl peroxide.
  • Peresters and peroxy carbonates butyl peracetate, cumyl peracetate, cumyl perpropionate, cyclohexyl peracetate, di-t-butyl peradipate, di-t-butyl perazelate, di-t-butyl perglutarate, di-t-butyl perthalate, di-t-butyl persebacate, 4-nitrocumyl perpropionate, 1-phenylethyl perbenzoate, phenylethyl nitro-perbenzoate, t-butylbicyclo-(2,2,1)heptane percarboxylate, t-butyl-4-carbomethoxy perbutyrate, t-butylcyclobutane percarboxylate, t-butylcyclohexyl peroxycarboxylate, t-butylcyclopentyl percarboxylate, t-butylcyclopropane percarboxylate, t-but
  • the unmodified polypropylene (A) to prepare such a high melt strength polypropylene (HMS-PP) has preferably an MFR 2 (230 °C) in a range of 0.05 to 45.00 g/10 min. More preferably the MFR 2 (230 °C) is in a range of 0.05 to 35.00 g/10 min in case the unmodified polypropylene (A) is a homopolymer. On the other hand the MFR 2 (230 °C) is in a range of 0.05 to 45.00 g/10 min in case the unmodified polypropylene (A) is a copolymer.
  • the unmodified polypropylene (A) is a homopolymer.
  • the expression homopolymer used in the instant invention relates to a polypropylene that consists substantially, i.e. of more than 99 wt.-%, still more preferably of at least 99.8 wt.-% of propylene units. In a preferred embodiment only propylene units in the propylene homopolymer are detectable.
  • the comonomer content can be determined with FT infrared spectroscopy, as described below in the examples.
  • the high melt strength polypropylene is produced from the unmodified polypropylene (A) as defined above under process conditions as defined in detail below.
  • polypropylene composition comprises at least one ⁇ -nucleating agent (N).
  • any ⁇ -nucleating agent (N) can be used.
  • Suitable ⁇ -nucleating agents (N) are selected from the group consisting of
  • Such additives are generally commercially available and are described, for example, in Gachter/Muller, Plastics Additives Handbook, 4th Edition, Hansa Publishers, Kunststoff, 1993 .
  • the ⁇ -nucleating agent (N) content of the polypropylene composition is preferably up to 5 wt.-%.
  • the polypropylene composition of the present invention contain from 0.0001 to 1.0 wt.-%, preferably from 0.0005 to 0.50 wt.-%, of a ⁇ -nucleating agent (N), in particular selected from the group consisting of dibenzylidenesorbitol (e.g. 1,3 : 2,4 dibenzylidene sorbitol), dibenzylidenesorbitol derivative, preferably dimethyldibenzylidenesorbitol (e.g.
  • substituted nonitol-derivatives such as 1,2,3,-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.
  • the most preferred ⁇ -nucleating agents (N) are 1,2,3,-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer and vinylalkane polymer.
  • the ⁇ -nucleating agent (N) is 1,2,3,-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer and vinylalkane polymer.
  • the ⁇ -nucleating agent (N) is
  • ⁇ -nucleating agents (N) are polymeric ⁇ -nucleating agents selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers
  • these polymeric nucleating agents are either accomplished by a special reactor technique, where the catalyst is prepolymerised with monomers like e.g. vinylcyclohexane (VCH), or by blending the polypropylene composition with the vinylcycloalkane polymer or vinylalkane polymer.
  • VCH vinylcyclohexane
  • the polymeric nucleating agent (N) is introduced into the propylene copolymer (C-PP) by blending or even more prefered by the specific reactor technique as defined below. Accordingly in one embodiment of the present invention the ⁇ -nucleating agent (N) is introduced into the instant polypropylene composition as part of the propylene copolymer (C-PP).
  • the required components as defined above may be present in specific amounts within the new polypropylene composition.
  • the polypropylene composition according to the instant invention comprises
  • the polypropylene composition of the present invention may comprise further components.
  • the polypropylene composition comprises as polymer components only the propylene copolymer (C-PP) and the high melt strength polypropylene (HMS-PP) as defined above. Accordingly the amounts of the propylene copolymer (C-PP), the high melt strength polypropylene (HMS-PP) and the ⁇ -nucleating agent (N) may not result in 100 wt.-% based on the total polypropylene composition. Thus the remaining part up 100.0 wt.-% may be accomplished by further additives known in the art.
  • the inventive polypropylene composition may comprise additionally small amounts of stabilizers, acid scavengers, lubricants and mold release agents, nucleating agents, antistatics, plasticizers, dyes or pigments. In general, these are incorporated during pelletization of the pulverulent product obtained in the polymerization.
  • the present invention is also directed to the use of the above defined polypropylene composition.
  • the polypropylene composition as defined in the instant invention is used for the preparation of molded products, like extrusion blown molded products.
  • the present invention is directed to the use of the polypropylene composition of the instant invention to improve the impact preferomance (drop test) by keeping the gloss on a high level of extrusion blown molded articles, like extrusion blown molded bottles, made out of said polypropylene composition compared to conventional extrusion blown molded bottles, in particular compared to extrusion blown molded bottles made out of the comparative examples CE1 and CE2, respectively.
  • the present invention is directed to molded articles, like extrusion blown molded articles, comprising, preferably comprising at least 90 wt.-%, more preferably consisting of, a polypropylene composition according to this invention. More particularly the present invention is directed to bottles produced by an extrusion blown process comprising, preferably comprising at least 90 wt.-%, more preferably consisting of, a polypropylene composition according to this invention.
  • the propylene copolymer (C-PP) as defined in the instant invention may be prepared by polymerizing, in a slurry reactor, for example a loop reactor, propylene optionally together with at least another C 2 to C 12 ⁇ -olefin (comonomers), in the presence of a polymerization catalyst to produce a part of the propylene copolymer (C-PP).
  • This part is then transferred to a subsequent gas phase reactor, wherein in the gas phase reactor propylene is reacted in the presence of suitably selected other C 2 to C 12 ⁇ -olefin(s) (comonomers) in order to produce a further part in the presence of the reaction product of the first step.
  • This reaction sequence provides a reactor blend of parts (i) (fraction (A)) and (ii) (fraction (B)) constituting a propylene copolymer (C-PP). It is of course possible by the present invention that the first reaction is carried out in a gas phase reactor while the second polymerization reaction is carried out in a slurry reactor, for example a loop reactor. It is furthermore also possible to reverse the order of producing parts (i) and (ii), which has been described above in the order of first producing part (i) and then producing part (ii).
  • the above-discussed process comprising at least two polymerization steps, is advantageous in view of the fact that it provides easily controllable reaction steps enabling the preparation of a desired reactor blend.
  • the polymerization steps may be adjusted, for example by appropriately selecting monomer feed, comonomer feed, hydrogen feed, temperature and pressure in order to suitably adjust the properties of the polymerization products obtained. It is in particular possible to obtain a multimodality, preferably the bimodality, of the propylene copolymer (C-PP), with respect to the comonomer, like ethylene, distribution as well as with respect to the molecular weights and MFR 2 (230 °C) values during said multistage polymerization procedures.
  • C-PP propylene copolymer
  • Such a process can be carried out using any suitable catalyst for the preparation of the propylene copolymer (C-PP).
  • a Ziegler-Natta catalyst in particular a high yield Ziegler-Natta catalyst (so-called fourth and fifth generation type to differentiate from low yield, so called second generation Ziegler-Natta catalysts).
  • a suitable Ziegler-Natta catalyst to be employed in accordance with the present invention comprises a catalyst component, a co-catalyst component and at least one electron donor (internal and/or external electron donor, preferably at least one external donor).
  • the catalyst component is a Ti-Mg-based catalyst component and typically the co-catalyst is an Al-alkyl based compound.
  • Suitable catalysts are in particular disclosed in US 5,234,879 , WO 92/19653 , WO 92/19658 and WO 99/33843 .
  • Preferred external donors are the known silane-based donors, such as dicyclopentyl dimethoxy silane or cyclohexyl methyldimethoxy silane.
  • a loop-gas phase process such as developed by Borealis, known as Borstar ® technology, described for example in EP 0 887 379 A1 and WO 92/12182 .
  • the reaction product of the slurry polymerization which preferably is carried out in a loop reactor, is then transferred to the subsequent gas phase reactor, wherein the temperature preferably is within the range of from 50 to 130 °C, more preferably 80 to 100 °C, at a pressure in the range of from 5 to 50 bar, preferably 15 to 35 bar, again with the option of adding hydrogen in order to control the molecular weight.
  • the residence time can vary in the reactor zones identified above.
  • the residence time in the slurry reaction for example the loop reactor, is in the range of from 0.5 to 5 hours, for example 0.5 to 2 hours, while the residence time in the gas phase reactor generally will be from 1 to 8 hours.
  • the properties of the random propylene copolymer (C-PP) produced with the above-outlined process may be adjusted and controlled with the process conditions as known to the skilled person, for example by one or more of the following process parameters: temperature, hydrogen feed, comonomer feed, propylene feed, catalyst, type and amount of external donor, split between two or more components of a multimodal polymer.
  • the high melt strength polypropylene (HMS-PP) is preferably obtained by a process as described in EP 0 879 830 A1 and EP 0 890 612 A2 . Both documents are herewith included by reference. Accordingly the high melt strength polypropylene (HMS-PP) is produced by
  • the process for producing the high melt strength polypropylene (HMS-PP) preferably is a continuous method, performed in continuous reactors, mixers, kneaders and extruders. Batchwise production of the high melt strength polypropylene (HMS-PP), however is feasible as well.
  • Practical sorption times ⁇ of the volatile bifunctional monomers range from 10 to 1000 s, where sorption times ⁇ of 60 to 600 are preferred.
  • the polymer composition in accordance with the present invention may be prepared by compounding the components within suitable melt mixing devices for preparing polymeric compounds, including in particular extruders single screw extruders as well as twin screw extruders.
  • suitable melt mixing devices include planet extruders and single screw co-kneaders.
  • twin screw extruders including high intensity mixing and kneading sections.
  • Suitable melt temperatures for preparing the compositions are in the range from 170 to 300 °C, preferably in the range from 200 to 260 °C, and at a throughput of 10 to 500 kg/h and a screw speed of 50 to 200 rpm.
  • the polypropylene composition or the propylene copolymer (C-PP) in accordance with the present invention is subjected a visbreaking step.
  • the visbreaking may be carried out in any known manner, but typically the present invention envisages chemical visbreaking using a peroxide visbreaking agent.
  • Typical visbreaking agents are 2,5-dimethyl-2,5-bis(tert.butyl-peroxy)hexane (DHBP) (for instance sold under the tradenames Luperox 101 and Trigonox 101), 2,5-dimethyl-2,5-bis(tert.butyl-peroxy)hexyne-3 (DYBP) (for instance sold under the tradenames Luperox 130 and Trigonox 145), dicumyl-peroxide (DCUP) (for instance sold under the tradenames Luperox DC and Perkadox BC), ditert.butyl-peroxide (DTBP) (for instance sold under the tradenames Trigonox B and Luperox Di), tert.butyl-cumyl-peroxide (BCUP) (for instance sold under the tradenames Trigonox T and Luperox 801) and bis (tert.butylperoxy-isopropyl)benzene (DIPP) (for instance sold under the tradenames Perkadox 14S and Luperox
  • Suitable amounts of peroxide to be employed in accordance with the present invention are in principle known to the skilled person and can easily be calculated on the basis of the amount of polypropylene composition and/or random propylene copolymer (C-PP) to be subjected to visbreaking, the MFR 2 (230 °C) value of the polypropylene composition and/or the propylene copolymer (C-PP) to be subjected to visbreaking and the desired target MFR 2 (230 °C) of the product to be obtained.
  • typical amounts of peroxide visbreaking agent are from 0.005 to 0.5 wt.-%, more preferably from 0.01 to 0.2 wt.-%, based on the amount of propylene polymer employed.
  • visbreaking in accordance with the present invention is carried out in an extruder, so that under the suitable conditions, an increase of melt flow rate is obtained.
  • higher molar mass chains of the starting product are broken statistically more frequently than lower molar mass molecules, resulting in an overall decrease of the average molecular weight and an increase in melt flow rate.
  • the NMR-measurement was used for determining the mm triad concentration in a manner well known in the art.
  • Randomness random ethylene (-P-E-P-) content / the total ethylene content x 100%.
  • M n Number average molecular weight
  • M w weight average molecular weight
  • MFD molecular weight distribution
  • SEC size exclusion chromatography
  • the oven temperature is 140 °C.
  • Trichlorobenzene is used as a solvent (ISO 16014).
  • MFR 2 (230 °C) is measured according to ISO 1133 (230 °C, 2.16 kg load)
  • Ethylene content is measured with Fourier transform infrared spectroscopy (FTIR) calibrated with 13 C-NMR.
  • FTIR Fourier transform infrared spectroscopy
  • a thin film of the sample was prepared by hot-pressing.
  • the area of absorption peaks 720 and 733 cm -1 was measured with Perkin Elmer FTIR 1600 spectrometer.
  • the method was calibrated by ethylene content data measured by 13 C-NMR. Content of any one of the C4 to C20 ⁇ -olefins is determined with 13 C-NMR; literature: " IR-Spektroskopie für Anwender"; WILEY-VCH, 1997 and “ Validierung in der Analytik", WILEY-VCH, 1997
  • C(C) is the comonomer content [in wt.-%] measured by Fourier transform infrared spectroscopy (FTIR) of the product obtained after the second reactor, i.e. the propylene copolymer (C-PP)
  • C(B) is the calculated comonomer content [in wt.-%] of the second propylene copolymer fraction (B).
  • the xylene cold solubles (XCS, wt.-%): Content of xylene cold solubles (XCS) is determined at 23 °C according ISO 6427.
  • the gel content is assumed to be identical to the xylene hot insoluble (XHI) fraction, which is determined by extracting 1 g of finely cut polymer sample with 350 ml xylene in a Soxhlet extractor for 48 hours at the boiling temperature. The remaining solid amount is dried at 90°C and weighed for determining the insolubles amount.
  • XHI xylene hot insoluble
  • strain hardening behaviour is determined by the method as described in the article " Rheotens-Mastercurves and Drawability of Polymer Melts", M. H. Wagner, Polymer Engineering and Sience, MID-APRIL 1SW, Vol. 36, NO. 7, pages 925 to 935 .
  • the content of the document is included by reference.
  • Figure 1 shows a schematic representation of the experimental procedure which is used to determine strain hardening.
  • the strain hardening behaviour of polymers is analysed by Rheotens apparatus (1) (product of Göttfert, Siemensstr.2, 74711 Buchen, Germany) in which a melt strand (2) is elongated by drawing down with a defined acceleration.
  • the haul-off force F in dependence of draw-down velocity v is recorded.
  • the test procedure is performed in a standard conditioned room with controlled room temperature of 23 °C and 1 atm.
  • the Rheotens apparatus (1) is combined with an extruder/melt pump (3) for continuous feeding of the melt strand (2).
  • the extrusion temperature is 200 °C; a capillary die with a diameter of 2 mm and a length of 6 mm is used.
  • the strength length between the capillary die and the Rheotens wheels is 80 mm.
  • the take-up speed of the Rheotens wheels was adjusted to the velocity of the extruded polymer strand (tensile force zero): Then the experiment was started by slowly increasing the take-up speed of the Rheotens wheels until the polymer filament breaks.
  • the acceleration of the wheels was small enough so that the tensile force was measured under quasi-steady conditions.
  • the acceleration of the melt strand (2) drawn down is 120 mm/sec 2 .
  • the Rheotens was operated in combination with the PC program EXTENS.
  • This is a real-time data-acquisition program, which displays and stores the measured data of tensile force and drawdown speed.
  • the schematic diagram in figure 1 shows in an exemplary fashion the measured increase in haul-off force F (i.e. "melt strength") versus the increase in draw-down velocity v (i.e. "drawability").
  • the drop test is performed on extrusion blow moulded 11 bottles, having an outer diameter of 90 mm, wall thickness: 0,6 mm; overall-height of 204 mm, height of the cylindrical mantle of 185 mm.
  • the bottles are filled up to their shoulder with water.
  • the estimated falling height is determined on 10 bottles.
  • the final test is to be performed on 20 bottles, starting at the pre-determined falling height. For each run 2 bottles are dropped.
  • next dropping height is chosen to be lower/same/higher for the next round.
  • the increase or decrease in height is 0,25 m, only at dropping heights ⁇ 1,5 m the increase or decrease is 0,1 m.
  • the bottles It is measured on the outer wall of the bottles. The top and bottom of the bottles is cut off. This round wall is then split in two, horizontally. Then the haze measurement and the wall thickness are done in six places around this wall, close to the middle. Then the haze value is reported as average of this six parallels.
  • the bottles are identical to The bottles:
  • compositions PP1 and PP2 have been produced in a BorstarTM-type two-step polymerization process starting in a prepolymerization reactor, followed by polymerization in a bulk-phase loop reactor, again followed by polymerization in a gas phase reactor, varying the molecular weight and ethylene content by appropriate hydrogen and comonomer feeds.
  • the catalyst used in the polymerization process was the commercial BCF20P catalyst (1.9 wt.-% Ti-Ziegler-Natta-catalyst as described in EP 591 224 ) of Borealis with triethylaluminium (TEA) as co-catalyst and dicyclo pentyl dimethoxy silane (donor "D") as donor.
  • TEA triethylaluminium
  • donor "D" dicyclo pentyl dimethoxy silane
  • the catalyst was prepolymerized with vinyl cyclohexane in an amount to achieve a concentration of 200 ppm poly(vinyl cyclohexane) (PVCH) in the final polymer.
  • PVCH poly(vinyl cyclohexane)
  • the prepolymeritsation with propylene was performed in a stirred tank reactor in liquid phase. Following a transfer to the loop raeactor, the first copolymer fraction (A) was produced with the parameters in the upper part of table 1, then the polymer was again transferred to the gas phase reactor and the second copolymer fraction (B) was produced with the parameters in the lower part of table 1.
  • An additive combination of 2000 ppm of Irganox B 225 supplied by Ciba Speciality Chemicals, a blend of 50 % Irganox 1010, Pentaerythrityl-tetrakis(3-(3',5'-di-tert. butyl-4-hydroxyphenyl)-propionate, CAS-no.
  • Table 1 Polymerization conditions Composition PP1 PP2 Catalyst feed [g/h] 1.02 0.93 Al/Ti ratio [mol/mol] 663 725 Al/donor ratio [mol/mol] 5.5 5.0 Prepolymerization Temperature [°C] 35 35 Pressure [kPa] 4700 4700 Residence time [h] 0.34 0.34 Loop reactor Temperature [°C] 70 68 Pressure [kPa] 4990 4970 H 2 /C 3 ratio [mol/kmol] 1.9 2.2 C 2 /C 3 ratio [mol/kmol] 6.0 8.4 Residence time [h] 0.50 0.49 Production rate [kg/h] 32.9 32.6 Gas phase reactor Temperature [°C] 70 70 Pressure [kPa] 2120 2160 H 2 /C 3 ratio [mol/kmol] n.d.
  • the components were blended according to Table 3.
  • a conventional additive package has been used like 0.2 wt/% Irganox B225 (antioxidant masterbatch supplied by Ciba Specialty Chemicals, Switzerland) and 0,05 wt% Ca-Stearate (CAS-No. 1592-23-0).
  • peroxide initiator Trigonox 101, supplied by Akzo Nobel
  • Blending took place in a twin screw extruder (PRISM TSE24 L/D ratio 40) with two high intensity mixing segments at temperatures between 190 and 240°C at a throughput of 10 kg/h and a screw speed of 50 rpm.
  • the material was extruded to two circular dies of 3 mm diameter into a water bath for strand solidification and then pelletized and dried.
  • RB307MO is the commercial random propylene ethylene copolymer of Borealis with an ethylene content of 3.9 wt.-%, an MFR 2 (230 °C) of 1.5 g/10min, and xylene cold soluble fraction (XCS) of 7.0 wt.-%.
  • HMS is the commercial high melt strength polypropylene DaployTM WB180HMS of Borealis based on a propylene homopolymer, wherein the high melt strength polypropylene DaployTM WB180HMS has a density of 905 kg/m 3 , a melting point of 165 °C, an MFR 2 (230°C) of 6.0 g/10 min, a melt strength of 11.5 cN at a maximum speed of 242 mm/s, a xylene cold soluble fraction (XCS) of 2.5 wt.-% and a branching index g' of 0.64.
  • XCS xylene cold soluble fraction
  • ⁇ is the commercial ⁇ -nucleating agent Millad NX 8000 (1,2,3,-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol)

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EP10160474.2A 2010-04-20 2010-04-20 Polyproylenflaschen Active EP2386604B1 (de)

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US9802394B2 (en) 2013-10-11 2017-10-31 Borealis Ag Machine direction oriented film for labels
US9828698B2 (en) 2013-12-04 2017-11-28 Borealis Ag Phthalate-free PP homopolymers for meltblown fibers
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US10100185B2 (en) 2014-02-06 2018-10-16 Borealis Ag Soft copolymers with high impact strength
US10100186B2 (en) 2014-02-06 2018-10-16 Borealis Ag Soft and transparent impact copolymers
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US10450451B2 (en) 2014-05-20 2019-10-22 Borealis Ag Polypropylene composition for automotive interior applications
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WO2013092624A1 (en) * 2011-12-23 2013-06-27 Borealis Ag Propylene copolymer for blow molded articles
US9969821B2 (en) 2011-12-23 2018-05-15 Borealis Ag Propylene copolymer for blow molded articles
AU2014270633B2 (en) * 2013-05-22 2016-06-02 Borealis Ag Polypropylene for film applications
WO2014187686A1 (en) * 2013-05-22 2014-11-27 Borealis Ag Polypropylene for film applications
RU2648675C2 (ru) * 2013-05-22 2018-03-28 Бореалис Аг Полипропилен для применения в пленках
EP3013902B1 (de) 2013-06-26 2018-11-28 Borealis AG Propylencopolymer für extrusionsblasgeformte flaschen
US20160145366A1 (en) * 2013-06-26 2016-05-26 Borealis Ag Propylene copolymer for extrusion blow molded bottles
US10202475B2 (en) * 2013-06-26 2019-02-12 Borealis Ag Propylene copolymer for extrusion blow molded bottles
WO2014206950A1 (en) * 2013-06-26 2014-12-31 Borealis Ag Propylene copolymer for extrusion blow molded bottles
RU2637930C2 (ru) * 2013-06-26 2017-12-08 Бореалис Аг Сополимер пропилена для бутылок, изготавливаемых пневмоформованием с экструзией
US9670347B2 (en) 2013-08-14 2017-06-06 Borealis Ag Propylene composition with improved impact resistance at low temperature
US9890275B2 (en) 2013-08-21 2018-02-13 Borealis Ag High flow polyolefin composition with high stiffness and toughness
US9777142B2 (en) 2013-08-21 2017-10-03 Borealis Ag High flow polyolefin composition with high stiffness and toughness
US10040930B2 (en) 2013-09-27 2018-08-07 Abu Dhabi Polymers Co. Ltd (Borouge) Llc. Polymer composition with high XS, high Tm suitable for BOPP processing
US9802394B2 (en) 2013-10-11 2017-10-31 Borealis Ag Machine direction oriented film for labels
JP2016535802A (ja) * 2013-10-24 2016-11-17 ボレアリス エージー バイモーダルランダムコポリマーに基づくブロー成形品
EP2865713A1 (de) * 2013-10-24 2015-04-29 Borealis AG Blasgeformter Artikel auf Basis eines bimodalen Random-Copolymers
US10519259B2 (en) 2013-10-24 2019-12-31 Borealis Ag Low melting PP homopolymer with high content of regioerrors and high molecular weight
US9708481B2 (en) 2013-10-24 2017-07-18 Borealis Ag Blow molded article based on bimodal random copolymer
WO2015059230A1 (en) * 2013-10-24 2015-04-30 Borealis Ag Blow molded article based on bimodal random copolymer
EA030785B1 (ru) * 2013-10-24 2018-09-28 Бореалис Аг Изделие, полученное экструзией с раздувом на основе бимодального неупорядоченного сополимера
KR20160058963A (ko) * 2013-10-24 2016-05-25 보레알리스 아게 바이모달 랜덤 공중합체 기반의 취입 성형 물품
US9751962B2 (en) 2013-11-22 2017-09-05 Borealis Ag Low emission propylene homopolymer with high melt flow
US9828698B2 (en) 2013-12-04 2017-11-28 Borealis Ag Phthalate-free PP homopolymers for meltblown fibers
US9637602B2 (en) 2013-12-18 2017-05-02 Borealis Ag BOPP film with improved stiffness/toughness balance
RU2648674C2 (ru) * 2013-12-18 2018-03-28 Бореалис Аг Изделие, изготовленное литьем с раздувом и обладающее хорошими механическими и оптическими свойствами
US10227427B2 (en) 2014-01-17 2019-03-12 Borealis Ag Process for preparing propylene/1-butene copolymers
US10100185B2 (en) 2014-02-06 2018-10-16 Borealis Ag Soft copolymers with high impact strength
US10100186B2 (en) 2014-02-06 2018-10-16 Borealis Ag Soft and transparent impact copolymers
US10030109B2 (en) 2014-02-14 2018-07-24 Borealis Ag Polypropylene composite
US10450451B2 (en) 2014-05-20 2019-10-22 Borealis Ag Polypropylene composition for automotive interior applications
US10501615B2 (en) 2015-01-23 2019-12-10 Total Research & Technology Feluy Bimodal polypropylene and process for the preparation thereof
WO2016116606A1 (en) * 2015-01-23 2016-07-28 Total Research & Technology Feluy Bimodal polypropylene and process for the preparation thereof
EP4682176A1 (de) * 2024-07-17 2026-01-21 Borealis GmbH Zufällige propylen-ethylen-copolymerzusammensetzungen mit zinkadipatkern
WO2026017726A1 (en) * 2024-07-17 2026-01-22 Borealis Gmbh Zinc adipate-nucleated propylene-ethylene random copolymer compositions

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CN102869719A (zh) 2013-01-09
KR20120138834A (ko) 2012-12-26
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US8709561B2 (en) 2014-04-29
WO2011131578A1 (en) 2011-10-27
AU2011244480A1 (en) 2012-11-08
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